Ferroelectric materials are currently some of the most widely applied material systems and are constantly generating improved functions with higher efficiencies. Advancements in poly(vinylidene fluoride) (PVDF)-based polymer ferroelectrics provide flexural, coupling-efficient, and multifunctional material platforms for applications that demand portable, lightweight, wearable, and durable features. We highlight the recent advances in fluoropolymer ferroelectrics, their energetic cross-coupling effects, and emerging technologies, including wearable, highly efficient electromechanical actuators and sensors, electrocaloric refrigeration, and dielectric devices. These developments reveal that the molecular and nanostructure manipulations of the polarization-field interactions, through facile defect biasing, could introduce enhancements in the physical effects that would enable the realization of multisensory and multifunctional wearables for the emerging immersive virtual world and smart systems for a sustainable future.